Designer substrate library for quantitative, predictive modeling of reaction performance

被引:62
作者
Bess, Elizabeth N. [1 ]
Bischoff, Amanda J. [1 ]
Sigman, Matthew S. [1 ]
机构
[1] Univ Utah, Dept Chem, Salt Lake City, UT 84112 USA
基金
美国国家科学基金会;
关键词
asymmetric catalysis; free-energy relationships; computational chemistry; ASYMMETRIC TRANSFER HYDROGENATION; GAUSSIAN-BASIS SETS; ROBUSTNESS SCREEN; RAPID ASSESSMENT; ARYL KETONES; ATOMS LI; SELECTIVITY; CATALYST; RHODIUM; ENANTIOSELECTIVITY;
D O I
10.1073/pnas.1409522111
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
Assessment of reaction substrate scope is often a qualitative endeavor that provides general indications of substrate sensitivity to a measured reaction outcome. Unfortunately, this field standard typically falls short of enabling the quantitative prediction of new substrates' performance. The disconnection between a reaction's development and the quantitative prediction of new substrates' behavior limits the applicative usefulness of many methodologies. Herein, we present a method by which substrate libraries can be systematically developed to enable quantitative modeling of reaction systems and the prediction of new reaction outcomes. Presented in the context of rhodium-catalyzed asymmetric transfer hydrogenation, these models quantify the molecular features that influence enantioselection and, in so doing, lend mechanistic insight to the modes of asymmetric induction.
引用
收藏
页码:14698 / 14703
页数:6
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